CN113637427A - Formaldehyde-free adhesive for plywood and preparation method thereof - Google Patents

Formaldehyde-free adhesive for plywood and preparation method thereof Download PDF

Info

Publication number
CN113637427A
CN113637427A CN202110946210.XA CN202110946210A CN113637427A CN 113637427 A CN113637427 A CN 113637427A CN 202110946210 A CN202110946210 A CN 202110946210A CN 113637427 A CN113637427 A CN 113637427A
Authority
CN
China
Prior art keywords
plywood
formaldehyde
free adhesive
agent
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110946210.XA
Other languages
Chinese (zh)
Inventor
朱玉国
赵康
李炳泉
唐立超
董春生
滕时飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Aquaset New Material Co ltd
Original Assignee
Jiangsu Aquaset New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Aquaset New Material Co ltd filed Critical Jiangsu Aquaset New Material Co ltd
Priority to CN202110946210.XA priority Critical patent/CN113637427A/en
Publication of CN113637427A publication Critical patent/CN113637427A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27DWORKING VENEER OR PLYWOOD
    • B27D1/00Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/06Manufacture of central layers; Form of central layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27DWORKING VENEER OR PLYWOOD
    • B27D1/00Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/08Manufacture of shaped articles; Presses specially designed therefor
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06Copolymers with styrene
    • C09J109/08Latex
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J111/00Adhesives based on homopolymers or copolymers of chloroprene
    • C09J111/02Latex
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02Homopolymers or copolymers of hydrocarbons
    • C09J125/04Homopolymers or copolymers of styrene
    • C09J125/08Copolymers of styrene
    • C09J125/14Copolymers of styrene with unsaturated esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04Homopolymers or copolymers of vinyl acetate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02Polyalkylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application discloses a formaldehyde-free adhesive for plywood. The formaldehyde-free adhesive product for the plywood comprises a main agent and a cross-linking agent, wherein the main agent comprises: water-based emulsion, polyhydric alcohol glycidyl ether, filler, auxiliary agent and water. The formaldehyde-free adhesive product for the plywood disclosed by the invention has the advantages of no formaldehyde release, long working life and opening time and good cohesiveness, can be used for preparing the plywood under the condition of not changing the existing mature preparation production line and process in the plywood industry, does not release formaldehyde in the obtained plywood, and overcomes the defect that the performance, process, environmental friendliness and the like of the existing formaldehyde-free adhesive applied to the plywood industry cannot be taken into consideration.

Description

Formaldehyde-free adhesive for plywood and preparation method thereof
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a formaldehyde-free adhesive for a plywood and a preparation method thereof.
Background
With the continuous improvement of the quality of life of people, some factors which are ignored by people before are more and more valued, wherein the pollution of indoor decoration is an extremely important aspect. The decoration pollution gas mainly comprises formaldehyde, benzene, toluene, ammonia and the like, wherein the formaldehyde is determined as carcinogenic and teratogenic substances by the world health organization. The formaldehyde is mainly from various indoor plywood sheets, and the formaldehyde released by the plywood sheets is mostly from formaldehyde adhesives in the plywood sheets. The formaldehyde adhesives, namely urea-formaldehyde resin, phenolic resin adhesive and melamine-urea-formaldehyde resin adhesive, are favored by plywood manufacturers due to excellent cohesiveness, manufacturability and high cost performance, and account for nearly 90% of the adhesive consumption in the plywood market.
At present, various adhesives for formaldehyde-free plywood are rapidly developed and continuously impact the market, and the formaldehyde-free adhesives are expected to be gradually replaced, so that a new hope is brought to the non-hydroformylation process of the industry, such as isocyanate non-formaldehyde adhesives, bio-based soybean adhesives and the like, and CN101524857A discloses a process for preparing the formaldehyde-free plywood by using isocyanate, wherein the process comprises a plurality of layers of single boards formed by combining adjacent layers in a cross structure or a parallel structure, a glue layer is arranged between the adjacent single boards, and the adhesive of the glue layer is isocyanate. The spray sizing method is adopted in the sizing procedure of the method, so that the sizing amount of the board is greatly reduced, the formaldehyde emission of the plywood is far lower than the relevant standard, however, the method directly uses pure pMDI as the curing agent, the reaction activity is high, the speed is high, the glue has short working life and high process requirement, and the quality stability of the product is influenced when the glue is applied to the plywood manufacturing and is slightly controlled badly. The bio-based soybean glue has poor stability, poor water resistance and higher mildew risk, the water resistance and mildew resistance are improved by some specific technologies in the related researches at present, but the obtained effect is limited, CN110982487A discloses a process for preparing aldehyde-free plywood by using aldehyde-free soybean protein adhesive with a multiple network structure, the bonding strength of the prepared 3-layer poplar plywood can only pass the requirement of II-type plywood, and the mildew resistance test is only observed for 15 days, so that the storage and use period of the adhesive which cannot meet the actual production requirement of a factory can be 3 months.
The method breaks through the industry tradition of 'no formaldehyde and no glue' in the plywood market, and the method is particularly urgent for preparing the formaldehyde-free adhesive for the plywood with excellent comprehensive performances such as cohesiveness, manufacturability, environmental friendliness and the like.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of the prior formaldehyde-free adhesive in the application of the adhesive in the plywood industry, such as: the invention provides a formaldehyde-free adhesive for plywood with excellent comprehensive performances such as cohesiveness, manufacturability, environmental protection and the like and a preparation method thereof, which are used in the plywood manufacturing industry.
The technical scheme is as follows: the invention provides a formaldehyde-free adhesive for plywood, which is divided into two components, namely a main agent and a cross-linking agent, wherein the main agent part of the product consists of the components except the cross-linking agent.
Specifically, the raw material formula of the formaldehyde-free adhesive for the plywood comprises the following components in parts by weight:
20-40 parts of water-based emulsion
50-100 parts of water
10-20 parts of polyol glycidyl ether
30-70 parts of filler
5-10 parts of thickening agent
0.1 to 0.5 portion of defoaming agent
0.2 to 0.5 portion of dispersant
6-40 parts of cross-linking agent
The aqueous emulsion is a product obtained by carrying out polymerization reaction on monomers and water at a certain temperature under the action of an emulsifier and an initiator, and comprises but is not limited to vinyl acetate-ethylene copolymer aqueous emulsion, polyvinyl acetate aqueous emulsion, acrylic polymer emulsion (including but not limited to vinyl acetate-ethylene copolymer aqueous emulsion, acrylic latex, organosilicon modified acrylic emulsion and the like), other rubber aqueous emulsion such as neoprene latex and the like, and all the emulsions are emulsions without benzene monomers such as styrene, methyl styrene and the like; further, the pH value of the emulsion of the invention is 4-8, more preferably 4-6; still further, the emulsions of the present invention have a Tg of between-20 ℃ and 25 ℃.
The polyhydric alcohol glycidyl ether is an oligomer with a main chain containing ether bonds (-R-O-R-), and an end group or a side group containing more than or equal to hydroxyl (-OH). It is prepared by ring-opening polymerization of low molecular weight polyol as initiator and olefin oxide under the action of catalyst. Such as glyceryl polyethers, polyoxypropylene diols and triols, polytetrahydrofuran diols, and the like.
Further, the present invention is preferably a glyceryl polyether, and further, the glyceryl polyether of the present invention is obtained by polymerizing glycerin and ethylene oxide, wherein different ethylene oxide is reacted with glycerin to obtain different products, the glyceryl polyether of the present invention preferably has 3 to 50, more preferably 7 to 31, and the glyceryl polyether having the ethylene oxide in the range of 7 to 31 may include, but is not limited to, glyceryl polyether-7, glyceryl polyether-8, glyceryl polyether-12, glyceryl polyether-15, glyceryl polyether-18, glyceryl polyether-20, glyceryl polyether-26, glyceryl polyether-31, etc. Further, the number of moles of ethylene oxide is preferably 12 to 18.
The fillers described herein include both inorganic and organic fillers. In the present invention, one or more of calcium carbonate, barium sulfate, white carbon black, clay, gypsum powder, talc powder, starch, flour, and wood powder are preferably mixed. Further, the inorganic filler of 800 mesh heavy calcium carbonate is preferable in the present invention.
The thickening agent comprises an inorganic thickening agent, a cellulose thickening agent, a polyacrylic acid thickening agent, a polyurethane thickening agent and the like. Further preferred are bentonite, attapulgite, montmorillonite, methyl cellulose, and carboxymethyl cellulose. Further, montmorillonite is preferred in the present invention.
The dispersants of the present invention include inorganic and organic dispersants. Further, the present invention preferably mixes one or more of water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, sodium polyacrylate, sodium lauryl sulfate, methylpentanol, and the like. Further, sodium polyacrylate salts are preferred in the present invention.
As the defoaming agent used in the aqueous coating product, a mineral oil type defoaming agent, a silicone type defoaming agent, a polyether type defoaming agent, a self-emulsifying defoaming agent and the like are generally used. However, the invention unexpectedly discovers that the use of polyether defoaming agent has better performance than the series defoaming agent, further, the preferable polyether defoaming agent has the molecular weight of more than or equal to 3000, hydroxyl functional groups of more than or equal to 3 and the solubility of more than or equal to 5g/L, and further, the preferable polyether GPE series defoaming agent is provided.
The cross-linking agent is aliphatic isocyanate, aromatic isocyanate and the like. Further, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (pMDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), and the like are preferable in the present invention.
The invention also discloses a preparation method of the formaldehyde-free adhesive for the plywood, which comprises the following specific steps:
1. sequentially adding water, a dispersing agent and a defoaming agent into a disperser, stirring for 3-5min, then adding a filler, stirring for 15-20min, sequentially adding polyol glycidyl ether, an aqueous emulsion and a thickening agent, and stirring for 10-15min to obtain a main agent part;
2. adding the cross-linking agent into the main agent component before bonding the plywood, stirring for 3-5min, and uniformly dispersing to obtain the formaldehyde-free adhesive for the plywood.
In addition, the invention also discloses a preparation method of the plywood, which comprises the following specific steps:
1. gluing the veneer with formaldehyde-free adhesive in a working life by using veneer gluing equipment, wherein the single-side gluing amount is 160-flour-added 280g/m2
2. And (3) carrying out veneer assembly on the glued veneers according to the odd layer principle and the fiber directions of the adjacent veneers are mutually vertical to obtain the veneer blank. Opening the slab, aging for 30-60min, and pre-pressing at 0.6-1.0MPa for 30-60 min;
3. and (3) hot-pressing the pre-pressed plate blank at the temperature of 110-.
Has the advantages that:
the formaldehyde-free adhesive product for the plywood disclosed by the invention has the advantages of no formaldehyde release, long working life and opening time and good cohesiveness, can be used for preparing the plywood under the condition of not changing the existing mature preparation production line and process in the plywood industry, does not release formaldehyde in the obtained plywood, and overcomes the defect that the performance, process, environmental friendliness and the like of the existing adhesive can not be considered when the adhesive is applied to the plywood industry.
Furthermore, the plywood prepared by the adhesive can pass a type I plywood dipping and stripping test, and the bonding strength is more than or equal to 1.0 Mpa;
furthermore, in order to meet the process requirements of plywood production, the working life of the adhesive is more than or equal to 60min, and the opening time is more than or equal to 60 min;
furthermore, all the raw materials of the invention are formaldehyde-free adhesives, and the formaldehyde-free adhesives belong to formaldehyde-free adhesives.
Detailed Description
In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments.
I test method
The pot life evaluation method comprises the following steps:
the adhesive is prepared, the viscosity of the adhesive is continuously tested by using a digital rotational viscometer at 25 ℃ under the condition of 60rpm of a 7# rotor, and the time T when the viscosity of the adhesive reaches 2 times of the initial test viscosity is recorded, namely the working life of the adhesive.
The evaluation method of the free formaldehyde emission of the adhesive comprises the following steps:
determination of 3.16 free formaldehyde content in GB/T14074-2017
The preparation method of the plywood of the embodiment of the invention comprises the following steps:
1. gluing the single board with formaldehyde-free adhesive in the use period with single board gluing equipment to obtain single board glue with single glue spreading amount of 180g/m2
2. And (3) carrying out veneer assembly on the glued veneers according to the odd layer principle and the fiber directions of the adjacent veneers are mutually vertical to obtain the veneer blank. Opening the plate blank, aging for 60min, and pre-pressing at 0.8MPa for 30 min;
3. and (3) carrying out hot pressing on the pre-pressed plate blank, wherein the hot pressing temperature is 120 ℃, the hot pressing time is 1min/mm calculated according to the thickness of the plate blank, and the hot pressing pressure is 0.8Mpa, so that the plywood product is obtained.
Method for evaluating open storage time:
1. preparing the adhesive;
2. gluing the veneers for assembly to obtain an assembled plywood;
3. sequentially pre-pressing the assembled plywood to obtain a pre-pressed board;
4. carrying out hot pressing and curing on the pre-pressed board to obtain a plywood sample board, and sawing the sample board to carry out dipping stripping and bonding strength test;
5. calculating the open display time: timing is carried out from the start of gluing the veneers to the end of prepressing the assembled veneers, meanwhile, the plywood sample plate passes the I-type dipping and stripping test, the gluing strength is more than or equal to 1.0Mpa, and the time is the opening and standing time.
The evaluation method of formaldehyde emission of the plywood comprises the following steps:
method for measuring 4.60 formaldehyde emission in GB/T17657-2013-1 m3 climate box
Adhesive adhesion evaluation method:
4.19.4 class I dip-stripping test in GB/T17657-2013
4.17 bond Strength determination in GB/T17657-2013, wherein specimen treatment is carried out as prescribed in GB/T17657-2013 at 4.17.5.2.3
II raw material
Figure BDA0003216735920000061
Figure BDA0003216735920000071
Figure BDA0003216735920000072
Figure BDA0003216735920000081
Example III
The formaldehyde-free adhesive for the plywood is prepared from the following components in parts by weight according to the preparation method:
Figure BDA0003216735920000082
Figure BDA0003216735920000091
Figure BDA0003216735920000101
Figure BDA0003216735920000111
Figure BDA0003216735920000112
Figure BDA0003216735920000121
IV results
The adhesive product prepared in the above example and 7-layer eucalyptus plywood with 2.2mm thickness of veneer prepared by the plywood preparation process by using the adhesive have the following detection results by the evaluation method:
Figure BDA0003216735920000122
Figure BDA0003216735920000131
note: the impregnation peel test example was not passed, and the adhesion strength was recorded as "0".
The adhesive and the plywood prepared by the adhesive disclosed by the invention have no formaldehyde detected, and the environmental protection performance is greatly improved compared with that of the traditional formaldehyde adhesive.
From the results of 9 groups of examples, i.e., examples 1 to 6, comparative examples 1, 2, 7, etc., it is understood that the adhesives prepared using the vinyl acetate-ethylene copolymer aqueous emulsion, the acrylic polymer emulsion, and the neoprene emulsion as the aqueous emulsion have a long pot life of more than 60min, the open-time aging time of more than 60min when the plywood is prepared using the adhesives, the plywood samples prepared using the adhesives can pass the I-type board dip-peel test, and the bonding strength is more than 1.0Mpa, while the adhesives prepared using the styrene-butadiene latex containing the benzene monomer and the styrene-acrylic emulsion and the adhesives prepared using the adhesives for preparing the plywood samples do not have the desired effects in terms of bonding performance and process.
From the results of 5 groups of examples 1 to 3, 8 and 9, it can be seen that even when the aqueous emulsion does not contain the benzene-based monomer, the adhesive prepared has a Tg too high (> 25 ℃) or too low (< 25 ℃), which makes the adhesive performance not pass the detection requirements.
From the results of the 4 groups of examples 1 to 3, comparative example 10 and the like, it can be seen that when the pH of the aqueous emulsion is too high (> 8), the pot life of the prepared adhesive is only 15min, and the bonding performance can not pass the detection requirement.
From the results of 3 groups of examples, namely example 1, comparative example 3, comparative example 4 and the like, it can be seen that the effect of adopting the defoaming agent GPE3000 is better than that of the defoaming agent NOPCO NXZ, the defoaming agent NOPCO NXZ is better than that of not adding the defoaming agent, the main influence is reflected on the bonding strength of the prepared plywood sample plate, and meanwhile, the opening aging time when the plywood sample plate is prepared is influenced to a certain extent.
From the results of 4 groups of examples, namely example 2, example 5, comparative example 6 and the like, it can be seen that the addition of the glyceryl polyether G-12 can significantly improve the open-time of the plywood sample when the plywood sample is prepared.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application.

Claims (10)

1. The formaldehyde-free adhesive for the plywood is characterized by comprising a main agent and a cross-linking agent, wherein the main agent comprises: water-based emulsion, polyhydric alcohol glycidyl ether, filler, auxiliary agent and water; the polyol glycidyl ether is an oligomer with a main chain containing ether bonds (-R-O-R-), and a terminal group or a side group containing more than 2 hydroxyl groups (-OH).
2. The formaldehyde-free adhesive for plywood according to claim 1, wherein the aqueous emulsion is 20 to 40 parts; 50-100 parts of water; 10-20 parts of polyhydric alcohol glycidyl ether; 30-70 parts of a filler; 5-10 parts of a thickening agent; 0.1-0.5 part of defoaming agent; 0.2-0.5 part of dispersant; 6-40 parts of a cross-linking agent.
3. The formaldehyde-free adhesive for plywood as claimed in claim 1, wherein said aqueous emulsion is a product obtained by polymerizing a monomer and water at a certain temperature under the action of an emulsifier and an initiator, and comprises: vinyl acetate-ethylene co-cluster water-based emulsion, polyvinyl acetate water-based emulsion, acrylic polymer emulsion and rubber water-based emulsion.
4. The formaldehyde-free adhesive for plywood as claimed in claim 1, wherein said aqueous emulsion is an emulsion containing no benzene-based monomer.
5. The formaldehyde-free adhesive for the plywood as recited in claim 1, wherein the pH value of the aqueous emulsion is 4-8; the Tg of the emulsion is between-20 and 25 ℃.
6. The formaldehyde-free adhesive of claim 1 wherein the glycidyl ether of a polyol is a glycerol polyether comprising: glyceryl polyether-7; glyceryl polyether-8; glyceryl polyether-12; glyceryl polyether-15; glyceryl polyether-18; glyceryl polyether-20; glyceryl polyether-26; glyceryl polyether-31.
7. The formaldehyde-free adhesive for plywood of claim 1 wherein said filler is: one or more of calcium carbonate, barium sulfate, white carbon black, pottery clay, gypsum powder, talcum powder, starch, flour and wood powder.
8. The formaldehyde-free adhesive for the plywood as claimed in claim 1, wherein the defoaming agent is a polyether defoaming agent, has a molecular weight of not less than 3000, has a hydroxyl functional group of not less than 3, and has a solubility of not less than 5 g/L.
9. The formaldehyde-free adhesive for plywood of claim 1 wherein said cross-linking agent is: toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (pMDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI).
10. The method for preparing the formaldehyde-free adhesive for the plywood as claimed in claim 1, wherein water, a dispersing agent and a defoaming agent are sequentially added into a disperser and stirred for 3-5min, then a filler is added and stirred for 15-20min, and then polyol glycidyl ether, an aqueous emulsion and a thickening agent are sequentially added and stirred for 10-15min to obtain a main agent part; adding the cross-linking agent into the main agent component before bonding the plywood, stirring for 3-5min, and uniformly dispersing to obtain the formaldehyde-free adhesive for the plywood.
CN202110946210.XA 2021-08-18 2021-08-18 Formaldehyde-free adhesive for plywood and preparation method thereof Pending CN113637427A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110946210.XA CN113637427A (en) 2021-08-18 2021-08-18 Formaldehyde-free adhesive for plywood and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110946210.XA CN113637427A (en) 2021-08-18 2021-08-18 Formaldehyde-free adhesive for plywood and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113637427A true CN113637427A (en) 2021-11-12

Family

ID=78422522

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110946210.XA Pending CN113637427A (en) 2021-08-18 2021-08-18 Formaldehyde-free adhesive for plywood and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113637427A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114248319A (en) * 2021-12-22 2022-03-29 江苏艾科赛特新材料有限公司 Preparation method of formaldehyde-free thick-core plywood

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003013027A (en) * 2001-06-28 2003-01-15 Sekisui Chem Co Ltd Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape
CN101693820A (en) * 2009-10-30 2010-04-14 北京化工大学 Methyl acrylate pressure-sensitive adhesive for LCD polarizer and preparation method thereof
CN110079248A (en) * 2019-04-30 2019-08-02 江苏艾科赛特新材料有限公司 A kind of aqueous no aldehyde adhesive and its application in wood-based plate
CN111205792A (en) * 2020-02-28 2020-05-29 上海宗特化工有限公司 Water-whitening-resistant water-based pressure-sensitive adhesive and preparation method thereof
CN111918945A (en) * 2019-03-07 2020-11-10 陶氏环球技术有限责任公司 Formaldehyde-free binder composition
CN112154192A (en) * 2018-07-04 2020-12-29 Sika技术股份公司 Chemically cross-linked water-based composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003013027A (en) * 2001-06-28 2003-01-15 Sekisui Chem Co Ltd Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape
CN101693820A (en) * 2009-10-30 2010-04-14 北京化工大学 Methyl acrylate pressure-sensitive adhesive for LCD polarizer and preparation method thereof
CN112154192A (en) * 2018-07-04 2020-12-29 Sika技术股份公司 Chemically cross-linked water-based composition
CN111918945A (en) * 2019-03-07 2020-11-10 陶氏环球技术有限责任公司 Formaldehyde-free binder composition
CN110079248A (en) * 2019-04-30 2019-08-02 江苏艾科赛特新材料有限公司 A kind of aqueous no aldehyde adhesive and its application in wood-based plate
CN111205792A (en) * 2020-02-28 2020-05-29 上海宗特化工有限公司 Water-whitening-resistant water-based pressure-sensitive adhesive and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114248319A (en) * 2021-12-22 2022-03-29 江苏艾科赛特新材料有限公司 Preparation method of formaldehyde-free thick-core plywood

Similar Documents

Publication Publication Date Title
CA2725896C (en) Carboxylated lignin based binders
CN102086367B (en) Plate alignment adhesive for surface plate lamination of engineered wood flooring and preparation method thereof
CN104479596B (en) Water-based environment-friendly plate splicing adhesive and preparation method thereof
Amen-Chen et al. Softwood bark pyrolysis oil-PF resols. Part 1. Resin synthesis and OSB mechanical properties
AU763902B2 (en) Adhesive composition for lignocellulose-type hot-pressed forms, and hot-pressed form production process using the same
CN101311200A (en) Method for preparing post-crosslinking modified urea-formaldehyde resin adhesive
CN109181612B (en) Water-resistant bio-based adhesive and preparation method thereof
US10844223B2 (en) Wood adhesive formulation
RU2606620C2 (en) LOW pH SOYA FLOUR UREA-FREE DILUENT AND METHODS OF MAKING SAME
KR102005767B1 (en) Wood adhesive formulation
CN113502138A (en) Two-component aldehyde-free adhesive composition of water-based acrylic emulsion
CN114058311B (en) Modified isocyanate adhesive and preparation method thereof, and formaldehyde-free molded tray and preparation method thereof
CN113637427A (en) Formaldehyde-free adhesive for plywood and preparation method thereof
CN111918945B (en) Formaldehyde-free adhesive composition
CN111662665B (en) Multi-component high-strength water-resistant composite adhesive and preparation method thereof
CN113831863B (en) Adhesive, preparation and application thereof
CN111635722B (en) Low-temperature curing ultralow-aldehyde water-resistant composite adhesive and preparation method thereof
JP5783888B2 (en) Adhesive composition for forming composite material with high water resistance, composite material, production method thereof, and adhesive for forming composite material with high water resistance
CN101974301B (en) Preparation method of bio oil-phenol-methanal copolycondensation resin wood adhesive
KR102705727B1 (en) Formaldehyde-free adhesive composition
CN114058300A (en) Preparation method of water-based formaldehyde-free wood adhesive composition
CN112048265A (en) Water-based adhesive and preparation method and application thereof
JP4109010B2 (en) Adhesive composition
JPS5846277B2 (en) adhesive composition
CN118813188A (en) Long-opening-time water-soluble formaldehyde-free adhesive and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20211112